ABSTRACT
Fluorenyl-alkynyl based π-conjugated rod-shaped oligomers bearing different central aromatic moieties and functionalizable di-alkynyl termini, such as H-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-H (OH1), H-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Btz-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-H (OH2) and H-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Btd-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-H (OH3) where Fl = 9,9-dioctylfluorene, Btz = N-hexylbenzotriazole, and Btd = benzothiadiazole, were successfully synthesized by a Pd(0) catalyzed Stille coupling protocol. Electron withdrawing benzothiadiazole and benzotriazole as strong to moderate acceptors and fluorene as the donor have been incorporated to adjust the Donor-Acceptor (D-A) strength for fine-tuning the bandgap (Eg) as well as the emission wavelength. The corresponding digold(i) σ-complexes (PPh3)Au-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Au(PPh3) (OM1), (PPh3)Au-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Btz-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Au(PPh3) (OM2) and (PPh3)Au-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Btd-[triple bond, length as m-dash]-Fl-[triple bond, length as m-dash]-Au(PPh3) (OM3) have also been prepared by a reaction of Au(PPh3)Cl and methanolic NaOMe in DCM with the corresponding alkynyl functionalized oligomers to take advantage of the heavy-atom effect on their emissive properties. The synthesized rod-shaped π-conjugated fluorene based oligomers and their binuclear Au(i) σ-complexes have been unambiguously characterized by various spectroscopic tools such as FTIR and multinuclear NMR as well as MALDI-TOF and CHN analyses. The absorption and emission spectral studies exhibited a progressive red shift with increasing the electron withdrawing character of the central aromatic unit. The rod-like oligomers having alkynyl termini and the corresponding digold(i) complexes are found to be blue, cyan and yellow emissive, demonstrating the fine-tuning of the emission wavelength. Most importantly, the fluorene based π-conjugated yellow light emitters OH3 and OM3 are successfully achieved by varying the donor/acceptor moiety to the fluorenyl-alkynyl backbone. The digold(i) diacetylide organometallic wires exhibit phosphorescence at 77 K in degassed CH2Cl2 due to the efficient intersystem crossing from the S1 to the T1 excited state as induced by heavy atoms.
